JP4862247B2 - Heat resistant adhesive composition - Google Patents

Description

  The present invention relates to a heat-resistant adhesive composition having excellent adhesiveness, and more specifically, it contains a solvent-soluble polyimide that is industrially extremely useful as an electronic material adhesive that requires high reliability and heat resistance. The present invention relates to a heat resistant adhesive composition.

  Conventionally, flexible wiring boards are often manufactured by bonding an aromatic polyimide film and a copper foil using an adhesive such as an acrylic resin, an epoxy resin, or a urethane resin. However, the flexible wiring board manufactured using such a conventionally known adhesive has a problem that the adhesive layer may be swollen or peeled off when exposed to a high temperature in the subsequent soldering process. Improvement of the heat resistance of the agent has been desired.

  In addition, NBR-containing adhesives are widely used as good adhesives with balanced properties such as peel strength, heat resistance, and insulation, but they have a major drawback in electrocorrosion (copper migration). Therefore, when the insulation resistance between the circuits is remarkably reduced or severe, there is a problem that the copper wire is connected to the copper wire.

  As a method for solving these problems, a method using a phase-separated adhesive composed of a siloxane-modified polyamideimide, an epoxy resin, and a rubber-based elastomer is disclosed (see Patent Document 1). However, although the adhesive used in this method is excellent in adhesiveness, the glass transition temperature is as low as around 220 ° C., and it does not reach the currently required high heat resistance of about 260 ° C. In addition, the adhesive composition using siloxane-based polyimide (see Patent Documents 2 and 3) has a problem that a softening temperature is 200 ° C. or less and a large amount of siloxane-based outgas is generated at a high temperature.

JP 2001-152125 A Japanese Patent Laid-Open No. 1-132631 Japanese Patent Laid-Open No. 5-331285

  It is an object of the present invention to provide a heat-resistant adhesive composition mainly composed of a solvent-soluble polyimide, which is highly useful industrially as an electronic material adhesive that requires high reliability and heat resistance. .

  As a result of intensive studies to solve the above problems, the present inventors have found that the adhesive composition having the following composition has high heat resistance and excellent adhesiveness as an electronic material adhesive. As a result, the present invention has been completed.

That is, the present invention provides the following heat-resistant adhesive composition.
Item 1 A heat-resistant adhesive composition containing at least two different molecular weights selected from solvent-soluble polyimides obtained by imidizing an aromatic tetracarboxylic dianhydride and an aromatic diamine, The heat resistant adhesive composition comprises (A) at least one polyimide having a peak weight average molecular weight of 1,000 to less than 50,000 in molecular weight distribution measurement of gel permeation chromatography (GPC) and (B) It contains at least one polyimide having a peak weight average molecular weight of 50,000 to 500,000, and the ratio of the component (A) to the component (B) is a weight ratio of (A) :( B) = 50. : 50-0.1: The range of 99.9 is a heat resistant adhesive composition characterized by the above-mentioned.

  Item 2 In the heat-resistant adhesive composition, the weight average molecular weight of the peak of the component (A) is 5,000 to 30,000, and the weight average molecular weight of the peak of the component (B) is 50,000 to 200,000. Item 2. The heat-resistant adhesive composition according to Item 1 above.

  Item 3. The heat-resistant adhesive composition according to Item 1 or 2, wherein the polymer terminal of the component (A) and the component (B) is an acid terminal and / or an amine terminal.

  Item 4. The heat-resistant adhesive composition according to Item 3, wherein the polymer terminal of the component (A) and the component (B) is an amine terminal.

  Item 5 The aromatic tetracarboxylic dianhydride is ethylene glycol bis-anhydro trimellitate, pyromellitic dianhydride, oxydiphthalic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic acid At least one selected from the group consisting of dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride The heat-resistant adhesive composition according to any one of Items 1 to 4, which is

  Item 6 The heat resistance according to Item 5, wherein the aromatic tetracarboxylic dianhydride is ethylene glycol-bis-anhydrotrimellitate or 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride. Adhesive composition.

  Item 7 The aromatic diamine is 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl sulfone, 4,4′-diaminodiphenyl sulfide, 1,4-bis (4-aminophenoxy) benzene, 1,3- Bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 4 , 4′-bis (4-aminophenoxy) biphenyl, 4,4′-bis (3-aminophenoxy) biphenyl, bis [4- (4-a Item 7. The heat-resistant adhesive composition according to any one of Items 1 to 6, which is at least one selected from the group consisting of minophenoxy) phenyl] ether and bis [4- (3-aminophenoxy) phenyl] ether.

  Item 8 The aromatic diamine is 4,4′-diaminodiphenyl ether, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, bis [4- (4-aminophenoxy) phenyl] sulfone and bis [4 Item 8. The heat-resistant adhesive composition according to Item 7, which is at least one selected from the group consisting of-(4-aminophenylmethyl) phenyl] sulfone.

  Item 9 The aromatic tetracarboxylic dianhydride is ethylene glycol-bis-anhydrotrimellitate or 3,3 ′, 4,4′-diphenyltetracarboxylic dianhydride, and the aromatic diamine is 4, The above is at least one selected from the group consisting of 4'-diaminodiphenyl ether, 2,2-bis [4- (4-aminophenoxy) phenyl] propane and bis [4- (4-aminophenylmethyl) phenyl] sulfone Item 5. The heat-resistant adhesive composition according to any one of Items 1 to 4.

  Item 10 A polyimide varnish containing the heat-resistant adhesive composition according to any one of Items 1 to 9.

  Item 11 A polyimide copper clad laminate obtained by using the polyimide varnish according to Item 10.

  According to the present invention, a heat-resistant adhesive composition excellent in adhesiveness and heat resistance is provided as compared with conventional siloxane-modified polyimide adhesives. Taking advantage of such characteristics, it is suitably used as a heat-resistant adhesive between a copper foil and a heat-resistant material such as a heat-resistant film and an inorganic sheet. Moreover, the polyimide copper clad laminated board of this invention can be used for uses, such as a flexible wiring board, a wiring board for COF, and a wiring board for TAB.

The present invention will be described in detail below.
Heat-resistant adhesive composition The heat-resistant adhesive composition of the present invention has at least two different molecular weights selected from solvent-soluble polyimides obtained by imidizing an aromatic tetracarboxylic dianhydride and an aromatic diamine. A heat-resistant adhesive composition containing at least seeds, wherein the heat-resistant adhesive composition has a weight average molecular weight of 1,000 (A) peak in gel permeation chromatography (GPC) molecular weight distribution measurement. The ratio of (A) component and (B) component containing at least 1 type of polyimide of less than 50,000 and (B) at least 1 type of polyimide whose weight average molecular weight of a peak is 50,000-500,000 Is characterized in that (A) :( B) = 50: 50 to 0.1: 99.9 in weight ratio.

  The component (A) has a peak weight average molecular weight of 1,000 to less than 50,000, preferably in the range of 5,000 to 30,000, and the component (B) has a peak weight average molecular weight of 50,000. It is in the range of ˜500,000, preferably 50,000 to 200,000. In particular, the component (A) is preferably in the range of 5,000 to 30,000 and the component (B) is in the range of 50,000 to 200,000 in terms of excellent balance of solvent solubility, heat resistance, and adhesiveness.

  The repeating structural unit of the component (A) and the component (B) is not particularly limited as long as the weight average molecular weight of the component (A) and the component (B) is in the above range, and may be the same or different, and may be industrial. It is preferable that it is the same from a viewpoint. Moreover, as for (A) component and (B) component, both are not restricted to 1 type, and one or both may be multiple types.

  The polymer terminal of the component (A) and the component (B) may be either an acid terminal (of an acid anhydride residue) and / or an amine terminal, in particular, as the polymer terminal of the component (A) and the component (B). Is preferable in that the amine terminal is excellent in the effect of improving adhesiveness.

  The ratio of the component (A) to the component (B) is (A) :( B) = 50: 50 to 0.1: 99.9, preferably 20:80 to 0.1: 99. 9, especially 10:90 to 0.1: 99.9 is preferable in terms of adhesiveness. When the proportion of the component (A) is too large, the heat resistance and adhesiveness tend to be lowered, which is not preferable.

  In the present invention, the average molecular weight is a weight average molecular weight in terms of standard polyethylene glycol measured by gel permeation chromatography using a standard polyethylene glycol calibration curve.

  Specific examples of the aromatic tetracarboxylic dianhydride component used in the present invention include pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3. ', 4,4'-diphenylsulfonetetracarboxylic dianhydride, ethylene glycol-bis-anhydro trimellitate, 1,2-propylene glycol-bis-anhydro trimellitate, 1,3-propylene glycol-bis -Anhydrotrimellitate, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3 ', 4,4'-biphenyl Ether tetracarboxylic dianhydride, 3,3 ′, 4,4′-dimethyldiphenylsilane tetracarboxylic dianhydride, 3,3 ′, 4,4′-tetrafe Rusilanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 4,4 ′ -Bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3 ', 4,4'-perfluoro Isopropylidene diphthalic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis (triphenylphthalic acid) Dianhydride, bis (triphenylphthalic acid) -4,4'-diphenyl ether dianhydride, bis (triphenylphthalic acid) -4,4'-diphenylme Aromatic tetracarboxylic dianhydrides such as emissions dianhydride are exemplified.

  Among these, ethylene glycol-bis-anhydro trimellitate, pyromellitic dianhydride, oxydiphthalic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′ , 4,4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride and the like are preferable, and in particular, 3,3 ′, 4,4′-diphenylsulfone. Tetracarboxylic dianhydride and ethylene glycol-bis-anhydrotrimellitate are preferable in terms of solvent solubility, heat resistance, and adhesiveness. Among them, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic acid A dianhydride is particularly preferable in terms of heat resistance.

  These may be used alone or in combination of two or more.

  Furthermore, the aromatic tetracarboxylic dianhydride component can be used by replacing a part of the aromatic tetracarboxylic dianhydride component with an aliphatic or alicyclic tetracarboxylic dianhydride as long as the effects of the present invention are not impaired. Specific examples of the aliphatic or alicyclic tetracarboxylic dianhydride include butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl- 1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 3,5,6- Tricarboxynorbonane-2-acetic acid dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 5- (2,5-dioxotetrahydrofural) -3-methyl-3-cyclohexene-1 , 2-dicarboxylic dianhydride, bicyclo [2.2.2] -oct-7-ene-2,3,5,6-tetracarboxylic dianhydride and the like.

  Specific examples of the aromatic diamine component used in the present invention include m-phenylenediamine, p-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylpropane, and 4,4′-diamino. Diphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'- Diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1 , 4-Bis (3-aminophenoxy) benzene, 1,3-bis 3-aminophenoxy) benzene, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl ] Propane, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 4,4′-bis (4-aminophenoxy) biphenyl, 4,4′-bis (3-aminophenoxy) biphenyl, bis Examples include [4- (4-aminophenoxy) phenyl] ether, bis [4- (3-aminophenoxy) phenyl] ether, and the like.

  Of these, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl sulfone, 4,4′-diaminodiphenyl sulfide, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4 -Aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (4-aminophenylmethyl) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2 -Bis [4- (3-aminophenoxy) phenyl] propane, 4,4'-bis (4-aminophenoxy) biphenyl, 4,4'- Sus (3-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] ether, bis [4- (3-aminophenoxy) phenyl] ether and the like are preferable, and 4,4′-diaminodiphenyl ether, 2 , 2-bis [4- (4-aminophenoxy) phenyl] propane, bis [4- (4-aminophenoxy) phenyl] sulfone, and bis [4- (4-aminophenoxy) phenyl] sulfone are solvent soluble and heat resistant. From the viewpoint of adhesiveness and adhesiveness. These may be used alone or in combination of two or more.

  Furthermore, an aromatic diamine component can be used by replacing a part of the aromatic diamine component with an aliphatic or alicyclic diamine as long as the effects of the present invention are not impaired. Specific examples of the aliphatic or alicyclic diamine include hexamethylenediamine, octamethylenediamine, decamethylenediamine, diaminocyclohexane, diaminodicyclohexylmethane, diaminodicyclohexylpropane, diaminobicyclo [2.2.1] heptane, and bis. (Aminomethyl) -bicyclo [2.2.1] heptane and the like are exemplified.

Method for Producing Heat Resistant Adhesive Composition The polyimide according to the heat resistant adhesive composition of the present invention can be produced from the aromatic tetracarboxylic dianhydride component and the aromatic diamine component according to a known method. .

  In the present invention, the molecular weight can be controlled by adjusting the molar ratio of the monomer components as in the case of a normal polycondensation polymer. That is, in the present invention, the amount of the aromatic diamine component and the amount of the aromatic tetracarboxylic dianhydride component used are 70 to 140 aromatic tetracarboxylic dianhydride components relative to the aromatic diamine component. From the range of mol%, it can be appropriately selected within the above range so as to obtain a desired value according to the required items such as the kind of polyimide, molecular weight, viscosity and the like. By using the aromatic diamine component in excess, the polymer ends of the polyimide can be made amine ends, while on the other hand, by using the aromatic tetracarboxylic dianhydride component in excess, it can be made acid ends.

  Examples of the method for producing these polyimides include a method of polycondensation reaction of an aromatic tetracarboxylic dianhydride component and an aromatic diamine component in an organic solvent. 1) Thermal imidization method in which water is heated in the presence of a small amount of azeotropic solvent to distill off the generated water out of the system by azeotropy; (2) After the polyamic acid of the polyimide precursor is produced, acetic anhydride, propionic anhydride Chemical imidization methods using dehydrating compounds such as acid anhydrides such as acid anhydrides and carbodiimide compounds such as dicyclohexylcarbodiimide

  Among the above polyimide production methods, the thermal imidization method is industrially preferable. For example, the aromatic tetracarboxylic dianhydride component and the aromatic diamine component are completely dissolved in an organic solvent, or the aromatic tetracarboxylic acid dicarboxylic acid is dissolved. A part of the anhydride component and / or aromatic diamine component is dissolved stepwise, and then heated to 100 to 250 ° C., preferably 150 to 200 ° C., and the generated water in the system is distilled off with an azeotropic solvent to depressurize. The method of carrying out a condensation reaction is mentioned, A solvent-soluble random copolymer or a block copolymer can be obtained by this method.

  As the organic solvent according to the present invention, an aprotic polar solvent is preferably used. Specifically, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, methyldiglyme, Examples include methyltriglyme, dioxane, tetrahydrofuran, cyclohexanone, cyclopentanone, and γ-butyrolactone, and these can be used alone or as a mixed system. Of these, N-methyl-2-pyrrolidone and γ-butyrolactone are particularly preferred from the viewpoint of polymerizability.

  Examples of the azeotropic solvent include aromatic hydrocarbons such as toluene, xylene, and solvent naphtha, and alicyclic hydrocarbons such as cyclohexane, methylcyclosexane, and dimethylcyclohexane. These are used alone or as a mixed system. be able to. The amount used is usually about 1 to 30% by weight, preferably about 5 to 10% by weight, based on the total amount of solvent.

  The reaction substrate concentration at this time is not particularly limited, but is in the range of 10 to 80% by weight, preferably 20 to 50% by weight from the viewpoint of workability and reaction efficiency.

The reaction time varies depending on the type of aromatic tetracarboxylic dianhydride component, the type of aromatic diamine component, and the molecular weight, but it is usually preferably 0.5 to 24 hours.
Yes.

  As the components (A) and (B) of the heat resistant adhesive composition according to the present invention, the imidization reaction of the aromatic tetracarboxylic acid component and the aromatic diamine component in the aprotic polar solvent as described above. The polyimide polymerization solution (varnish) obtained by the above can be used as it is, and xylene, dioxane, methyldiglyme and the like may be partially blended. Alternatively, the powdered polyimide may be reprecipitated and isolated from the polymerization solution, and the isolated polyimide powder may be uniformly re-dissolved in the aprotic polar solvent to prepare a varnish.

  The heat-resistant adhesive composition according to the present invention has, for example, (A) a polymerization solution having a peak weight average molecular weight of 1,000 to less than 50,000 and (B) a peak weight average molecular weight of 50 by the above-described production method. It can be produced by preparing a polymerization solution of 1,000,000 to 500,000 and mixing them. This makes it easy to prepare a coating solution having a desired weight ratio, and the formation of an adhesive layer can be suitably performed without any trouble, so that a polyimide varnish is optimal.

  In this case, the total content of the component (A) and the component (B) is preferably 1 to 50% by weight, particularly 5 to 30% by weight. From the same viewpoint, the B-type viscosity of the varnish at 25 ° C. is 0.1 to 500 Pa · s, preferably 1 to 100 Pa · s.

  Various additives such as a smoothing agent, a leveling agent, and a defoaming agent for obtaining surface smoothness can be added to the polyimide varnish as necessary.

Production of polyimide copper-clad laminate The copper-clad laminate of the present invention has a thickness through an adhesive layer (usually about 0.1 to 30 μm) containing thermoplastic polyimide as a main component on one side or both sides of a heat-resistant film. It has a structure in which 1 to 200 μm copper foil is laminated. Examples of the heat resistant film include aromatic polyester films (for example, polyethylene-2,6-naphthalene dicarboxylate), aromatic polyamide films, polyimide films, and the like. A polyimide film is most preferably used in that it is excellent in mutual balance of mechanical properties such as strength and various properties such as flexibility and low water absorption.

  As the polyimide used for the adhesive layer in the copper clad laminate of the present invention, it is preferable to use a resin mainly composed of thermoplastic polyimide in terms of excellent insulation and heat resistance (particularly, long-term heat resistance of 200 ° C. or higher). . The adhesive layer preferably has a glass transition temperature in the range of 180 to 320 ° C.

  Specific examples of the polyimide film include Upilex S, Upilex SGA, Upilex SN (trade name) manufactured by Ube Industries, Ltd., Kapton H, Kapton V, Kapton EN (trade name, manufactured by Toray DuPont Co., Ltd.), Apical AH. , Apical NPI, Apical HP (manufactured by Kaneka Chemical Co., Ltd., trade name) and the like. The surface of these resins may be subjected to plasma treatment, corona discharge treatment or the like. Although the thickness in particular of these polyimide films is not restrict | limited, The thing of 1-500 micrometers, Preferably the range of 1-100 micrometers can be used.

  A method for forming an adhesive layer on one side or both sides of these non-thermoplastic aromatic polyimide films will be described in detail. It can manufacture by apply | coating and drying the solution (varnish) of a thermoplastic polyimide directly on the said non-thermoplastic polyimide film. A varnish is a solution obtained by imidizing the aromatic tetracarboxylic dianhydride and an aromatic diamine in a solvent.

  As a method of directly coating on the non-thermoplastic polyimide film, known methods such as a die coater, a comma coater, a roll coater, a gravure coater, a curtain coater, and a spray coater can be employed. It can be suitably used depending on the thickness to be applied, the viscosity of the varnish, and the like.

  As a method for drying and curing the applied varnish, a normal heating and drying furnace can be used. As the atmosphere of the drying furnace, air, inert gas (nitrogen, argon) or the like can be used. Although it can select suitably as a drying temperature with the boiling point of a solvent, the temperature range of 60-400 degreeC is utilized suitably. The drying time can be appropriately selected depending on the thickness, concentration, and type of solvent, but it is desirable to carry out the drying in about 0.05 to 500 minutes.

Next, a method for thermocompression bonding a copper foil to the surface of the adhesive layer will be described. Although there is no restriction | limiting about the method of thermocompression bonding, For example, a hot press method and / or a thermal laminating method are mentioned as a typical method. As the hot press method, for example, the adhesive layer and the copper foil can be cut into a predetermined size of a press machine, overlapped, and thermocompression-bonded by a hot press. The heating temperature is 150 to 400 ° C, preferably 250 to 350 ° C. Although there is no restriction | limiting in particular as applied pressure, Preferably it can manufacture at 0.1-500 kg / cm < ² >. There is no restriction | limiting in particular as pressurization time.

  The polyimide copper-clad laminate provided by the present invention is subjected to each treatment such as roll winding, etching, and, in some cases, curl return, and then cut into a predetermined size if necessary. It can be used as a substrate for electronic parts. For example, it can be suitably used as a substrate of FPC, TAB, multilayer FPC, or flex-rigid substrate.

  Further, the heat-resistant adhesive composition of the present invention can be used as an insulating paint or metal coating as a solvent solution in which a polymerization solvent is replaced with a low boiling point solvent as a resin varnish in addition to the adhesive application of a copper clad laminate. It can also be used as an agent, a coating agent for plastics and films. Furthermore, as a molded object, it can use for various uses, such as insulating coatings, such as a base film of FPC or TAB, or an electric wire.

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. In addition, the measuring method of each characteristic in an Example and a comparative example and the abbreviation of a compound are as follows.
〔Measuring method〕
(1) Average molecular weight: by gel permeation chromatography (GPC) using N, N-dimethylformamide as a solvent, the number average molecular weight (Mn), weight average molecular weight (Mw) and polydispersity (Mw) in terms of standard polyethylene glycol / Mn).
(2) Viscosity (25 ° C.): Viscosity was measured using a B8H viscometer manufactured by Tokimec.
(3) Adhesive strength: The apparatus was measured using Instron (5565). Using a test piece obtained by cutting a copper-clad laminate into 1 cm × 8 cm, the measurement was allowed to stand in a temperature-controlled room at 25 ° C./60% RH for 2 hours or more, and then a copper foil and Kapton at one end were inserted with a jig, 50 mm / Peel peeling was performed at a tensile rate of min at 180 degrees, and the maximum peel strength was determined as the adhesive strength.
(4) Glass transition temperature: The glass transition temperature (Tg) of the adhesive layer is measured with a viscoelasticity measuring device.

[Abbreviation of compound]
DSDA: 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride BAPP: 2,2-bis [4- (4-aminophenoxy) phenyl] propane DPE: 4,4′-diaminodiphenyl ether NMP: N-methyl-2-pyrrolidone

[Production of solvent-soluble polyimide]
Production Example 1
3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride as an aromatic tetracarboxylic dianhydride in a four-necked flask equipped with a stirrer, a cooling tube, a thermometer, and a nitrogen gas introduction tube 106. 88 g (0.2983 mol), 2,2-bis [4- (4-aminophenoxy) phenyl] propane 85.90 g (0.2092 mol) as aromatic diamine, and 17.4 g (4. 4'-diaminodiphenyl ether). 0897 mol), 720 g of N-methyl-2-pyrrolidone as a reaction solvent, and 80 g of xylene as a dehydrating azeotropic solvent, the inside of the reaction system was purged with nitrogen, and the mixture was stirred at 180 ° C. in a nitrogen stream, and the generated water was removed from the system. While removing, a dehydration imidation reaction was performed for 5 hours to obtain a polyimide varnish a. The obtained polyimide varnish A was 20% by weight and the viscosity was 101.0 Pa · s (25 ° C.). Part of the obtained polyimide varnish is added to a large amount of methanol to precipitate a polymer powder, polymer filtered to isolate the polymer powder, washed with methanol, and vacuum dried at 60 ° C. for 8 hours to obtain a polyimide powder. It was. The molecular weight, polydispersity, and glass transition temperature of this polyimide powder were measured, and the results are shown in Table 1.

Production Examples 2-6
Each of the polyimide varnishes b to f was prepared in the same manner as in Production Example 1 except that DSDA was used in the amount shown in Table 1 as the aromatic tetracarboxylic acid component, and BAPP and DDE in the amounts shown in Table 1 were used as the diamine component. Manufactured. These polyimides were measured for molecular weight, polydispersity, and glass transition temperature, and the results are shown in Table 1.

Example 1
(Preparation of coating solution)
After adding 50 g of polyimide varnish b to 50 g of the polyimide varnish produced as described above and substituting with nitrogen, the mixture was stirred and mixed at 60 ° C. for 1 hour under a nitrogen stream to obtain a uniform polyimide varnish having a viscosity of 6.8 at 20% by weight. Obtained. The weight ratio of the polyimide varnish a and the polyimide varnish b at this time is 50:50.

[Production of polyimide copper-clad laminate]
The polyimide varnish was applied on a Kapton 100EN (manufactured by Toray DuPont Co., Ltd., thickness 25 μm) film to a thickness of about 25 μm, and dried under a nitrogen stream using a 200 ° C./25 min hot air dryer. After drying, a general rolled copper foil (thickness: 18 μm) was superimposed on the varnish-coated surface, and thermocompression bonded at 320 ° C. for 15 minutes under a pressure of 30 kg / cm ² to obtain a polyimide copper clad laminate. The adhesive strength of the obtained copper-clad laminate and the glass transition temperature (Tg) of the adhesive layer were measured, and the results are shown in Table 2.

Examples 2-11 and Comparative Examples 1-6
Using the soluble polyimides produced as described above, coating solutions having the blending weight ratios shown in Table 2 were prepared in the same manner as in Example 1. Table 2 shows the solution viscosity of each coating solution. A polyimide copper clad laminate was obtained in the same manner as in Example 1 except that the above coating solutions were used.
About these polyimide copper clad laminated boards, the adhesive strength and the glass transition temperature (Tg) of the contact bonding layer were measured, and the results are shown in Table 2.

  As is clear from Table 2, as the heat-resistant adhesive, those having two kinds of polyimides having different molecular weights as resin components have improved adhesiveness than those having two kinds of polyimides as individual components, Especially, the polymer terminal of two kinds of polyimides having an amine terminal is particularly excellent in the effect of improving adhesiveness.

According to the present invention, a solvent-soluble heat-resistant adhesive composition excellent in heat resistance and adhesiveness can be obtained, and in particular, it can be used in a wide range of applications as an adhesive for electronic materials that require these characteristics. In particular, it can be suitably used for laminating various metal foils such as copper foil and a heat-resistant support material (for example, a heat-resistant film or an inorganic sheet). Further, the polyimide copper clad laminate of the present invention is a wiring substrate such as a wiring board for COF, a wiring board for tape-automated bonding (TAB), a flexible printed wiring board, an IC package, and an LCD wiring board. Since it can be effectively used as an industrial product, it is extremely useful industrially.
Patent applicant New Nippon Rika Co., Ltd.

Claims (6)

Aromatic tetracarboxylic dianhydride is ethylene glycol bis-anhydro trimellitate, pyromellitic dianhydride, oxydiphthalic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride At least one selected from the group consisting of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride Aromatic diamine is 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl sulfone, 4,4′-diaminodiphenyl sulfide, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2- Bis [4- (3-aminophenoxy) phenyl] propane, 4,4′-bis (4-aminophenoxy) biphenyl, 4,4′-bis (3-aminophenoxy) biphenyl, bis [4- (4-amino An imidization reaction between an aromatic tetracarboxylic dianhydride and an aromatic diamine, which is at least one selected from the group consisting of phenoxy) phenyl] ether and bis [4- (3-aminophenoxy) phenyl] ether. A heat-resistant adhesive composition containing at least two kinds having different molecular weights selected from the solvent-soluble polyimide obtained, In the molecular weight distribution measurement of gel permeation chromatography (GPC), the adhesive composition is at least one polyimide having a weight average molecular weight of component (A) of 17,300 to 30,000 and a weight average of component (B). At least one type of polyimide having a molecular weight of 80,400 to 200,000 is mixed , and the ratio of the component (A) to the component (B) is (A) :( B) = 50: 50 to 1 by weight ratio. : range der 99 is, and, (a) component and the (B) heat-resistant adhesive composition which polymer terminal components, characterized in amine-terminated der Rukoto. The heat-resistant adhesive according to claim 1 , wherein the aromatic tetracarboxylic dianhydride is ethylene glycol-bis-anhydrotrimellitate or 3,3 ', 4,4'-diphenylsulfone tetracarboxylic dianhydride. Agent composition. Aromatic diamines are 4,4′-diaminodiphenyl ether, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, bis [4- (4-aminophenoxy) phenyl] sulfone and bis [4- ( The heat-resistant adhesive composition according to claim 1 , which is at least one selected from the group consisting of 4-aminophenylmethyl) phenyl] sulfone. The aromatic tetracarboxylic dianhydride is ethylene glycol-bis-anhydrotrimellitate or 3,3 ′, 4,4′-diphenyltetracarboxylic dianhydride, and the aromatic diamine is 4,4 ′. - diaminodiphenyl ether, 2,2-bis claim 1 is at least one selected from the group consisting of [4- (4-aminophenoxy) phenyl] propane and bis [4- (4-aminophenyl) phenyl] sulfone The heat-resistant adhesive composition described in 1. A polyimide varnish containing the heat-resistant adhesive composition according to claim 1 . A polyimide copper clad laminate obtained by using the polyimide varnish according to claim 5 .